Novel acidic porous clay heterostructure with highly ordered organic-inorganic hybrid structure: one-pot synthesis of mesoporous organosilica in the galleries of clay

A new class of organic-inorganic hybrid porous clay heterostructures (HPCHs) have been prepared through the surfactant-directed assembly of organosilica in the galleries of montmorillonite. The reaction involved hydrolysis and condensation of phenyltriethoxysilane and tetraethoxysilane in the presence of intragallery surfactant templates (dodecylame and cetyltrimethylammonium ion). The surfactant templates were removed from the pores by solvent-extraction. The products were characterized by X-ray diffraction (XRD), N-2 adsorption, solid-state Si-29 and C-13 NMR, and FTIR. XRD patterns indicated a regular interstratification of the clay layers for HPCHs. Depending on loading of phenyl groups, HPCHs had BET surface areas of 390-771 m(2) g(-1), pore volumes of 0.3-0.59 cm(3) g(-1), and the framework pore sizes in the supermicropore to small mesopore range (1.2-2.6 nm). HPCHs were hydrophobic and acidic.

Synthesis and characterization of polyethylene/clay-silica nanocomposites: A montmorillonite/silica-hybrid-supported catalyst and in situ polymerization

A novel approach to the preparation of polyethylene (PE) nanocomposites, with montmorillonite/silica hybrid (MT-Si) supported catalyst, was developed. MT-Si was prepared by depositing silica nanoparticles between galleries of the MT. A common zirconocene catalyst [bis(cyclopentadienyl)zirconium dichloride/methylaluminoxane] was fixed on the MT-Si surface by a simple method. After ethylene polymerization, two classes of nanofillers (clay layers and silica nanoparticles) were dispersed concurrently in the PE matrix and PE/clay-silica nanocomposites were obtained. Exfoliation of the clay layers and dispersion of the silica nanoparticles were examined with transmission electron microscopy. Physical properties of the nanocomposites were characterized by tensile tests, dynamic mechanical analysis, and DSC. The nanocomposites with a low nanofiller loading (<10 wt %) exhibited good mechanical properties. The nanocomposite powder produced with the supported catalyst had a granular morphology and a high bulk density, typical of a heterogeneous catalyst system.

Comparative study on the photoluminescent properties of siliceous MCM-41 with silica particles and xerogels

The samples of as-synthesized siliceous MCM-41, extracted MCM-41, amorphous silica particles and silica xerogels were heat treated from room temperature to 1000degreesC. Their photoluminescence (PL) spectra at room temperature excited by 254nm and 365nm ultraviolet light (UV) were investigated and compared. Excited by 254nm UV the MCM-41 samples do not display PL but amorphous silica particles and silica xerogels show PL, which changes with the heat treatment conditions for the samples. However, when excited by 365nm UV the PL spectra for the MCM-41 and the amorphous samples are similar. The carbon impurity and E' center mechanisms can be ruled out as the origin of PL in siliceous MCM-41 under UV excitation. The PL of MCM-41 series samples probably originates from oxygen-related defect center like dropSi-O-. according to the present work.

Preparation and luminescence properties of in situ formed lanthanide complexes covalently grafted to a silica network

Lanthanide-doped sol-gel-derived materials are an attractive type of luminescent materials that can be processed at ambient temperatures. However, the solubility of the lanthanide complexes in the matrix is a problem and it is difficult to obtain a uniform distribution of the complexes. Fortunately, these problems can be solved by covalently linking the lanthanide complex to the sol-gel-derived matrix. In this study, luminescent Eu3+ and Tb3+ bipyridine complexes were immobilized on sol-gel-derived silica. FT-IR, DTA-TG and luminescence spectra, as well as luminescence decay analysis, were used to characterize the obtained hybrid materials. The organic groups from the bipyridine-Si moiety were mostly destroyed between 220 and 600 degreesC. The luminescence properties of lanthanide bipyridine complexes anchored to the backbone of the silica network and the corresponding pure complexes were comparatively investigated, which indicates that the lanthanide bipyridine complex was formed during the hydrolysis and co-condensation of TEOS and modified bipyridine. Excitation at the ligand absorption wavelength (336 nm for the hybrid materials and 350 nm for the pure complexes) resulted in strong emission of the lanthanide ions: Eu3+ D-5(0)-F-7(J) (J = 0, 1, 2, 3, 4) and Tb3+ D-5(4)-F-7(J) (J = 6, 5, 4, 3) emission lines due to efficient energy transfer from the ligands to the lanthanide ions.

In situ synthesis of monodisperse luminescent terbium complex-silica nanocomposites

A facile strategy for the in situ synthesis of terbium complex-silica nanocomposites is described. The resultant spherical nanocomposites possess good monodispersity and exhibit luminescent properties of terbium complex.

Electrogenerated chemiluminescence sensing platform using Ru(bpy)(3)(2+) doped silica nanoparticles and carbon nanotubes

An effective electrogenerated chemiluminescence (ECL) sensor was developed by coimmobilization of the Ru(bpy)(2)(3+)-doped silica (RuDS) nanoparticles and carbon nanotubes (CNTs) on glassy carbon electrode through hydrophobic interaction. The uniform RuDS nanoparticles were prepared by a water-in-oil (W/O) microemulsion method and Ru(bpy)(3)(2+) doped inside could still maintain its high ECL efficiency. With such unique immobilization method, a great deal of Ru(bpy)(3)(2+) was immobilized three-dimensionally on the electrode , which could greatly enhance the ECL response and result in the increased sensitivity. On the other hand, CNTs played dual roles as matrix to immobilize RuDS nanoparticles and promoter to accelerate the electron transfer between Ru(bpy)(3)(2+) and the electrode. The as-prepared ECL sensor displayed good sensitivity and stability.

Macroporous fluoropolymeric films templated by silica colloidal assembly: A possible route to super-hydrophobic surfaces

A super-hydrophobic surface was obtained on a three-dimensional (313) polyvinylidene fluoride (PVDF) macroporous film. The porous films were fabricated through self-assembled silica colloidal templates. The apparent water contact angle of the surface can be tuned from 106 degrees to 153 degrees through altering the sintering temperature and the diameter of the colloidal templates. A composite structure of micro-cavities and nanoholes on the PVDF surface was responsible for the super-hydrophobicity. The wettability of the porous surfaces was described by the use of the Cassie-Baxter model and Wenzel's equation.

Luminescent hybrid films obtained by covalent grafting of terbium complex to silica network

Luminescent hybrid thin films consisting of terbium complex covalently bonded to a silica-based network have been obtained in situ via a sol-gel approach. A new monomer, N-(4-benzoic acid-yl), N'-(propylthiethoxysilyl)urea (PABI), has been synthesized by grafting isocyanatopropyltriethoxysilane (ICPTES) to p-aminobenzoic acid and characterized by H-1 NMR IR and MS, The monomer acts as a ligand for Tb3+ ion and as a sol-gel precursor. Band emission front Tb3+ ion due to an efficient ligand-to-metal energy transfer was observed by UV excitation. The decay curves of Tb3+ in the hybrid films were measured. The energy difference between the triplet state energy of PABI and the D-5(4) level of Tb3+ ion falls in the exciting range to sensitize Tb3+ ion fluorescence.

Preparation of polymer/silica nanoscale hybrids through sol-gel method involving emulsion polymers. II. Poly(ethyl acrylate)/SiO2

Poly(ethyl acrylate) (PEA)/SiO2 hybrids with different compositions were prepared under different casting temperatures and pH values. Their morphology as investigated by transmission electron microscopy (TEM) shows that samples with different compositions have different morphologies. When the SiO2 content is lower, PEA is the continuous phase and SiO2 is the dispersed phase. At higher SiO2 content, the change in phase morphology takes place, nd PEA gradually dispersing in the form of latex particles in SiO2 matrix. Change in phase morphology depends mainly on the time the sol-gel transition occurs. At suitable casting temperature and pH value, PEA/SiO2 in 95/5 and 50/50 hybrids with even dispersion was obtained.

Preparation of stable mesoporous silica FSM-16 from water glass in the presence of cetylpyridium bromide

The synthesis and characterization of the mesoporous materials FSM-16 (folded sheets mesoporous materials) with highly ordered structure in open-vessel by using cetylpyridium bromide (CPBr) and the single-layered polysilica Kanemite as new template and silicon source, respectively, has been investigated systematically. The hexagonal arrangements of uniformly size pores were characterized by FTIR. XRD. nitrogen adsorption. TG-DTA. SEM and TEM. Especially, the porous products with higher surface areas show remarkable thermal stability up to 1000 C. The potential application as carrier of catalysts or host-guest materials is anticipated. (C) 2001 Elsevier Science B.V. All rights reserved.

Size-dependent inelastic behavior of particle-reinforced metal-matrix composites

The strengthening behavior of particle-reinforced metal-matrix composites (MMCp) is primarily attributed to the dislocation strengthening effect and the load-transfer effect. To account for these two effects in a unified way, a new hybrid approach is developed in this paper by incorporating the geometrically necessary dislocation strengthening effect into the incremental micromechanical scheme. By making use of this hybrid approach, the particle-size-dependent inelastic deformation behavior of MMCp is given. Some comparisons with the available experimental results demonstrate that the present approach is satisfactory.

Net-like Ferromagnetic Mnsb Film Deposited on Porous Silicon Substrates

MnSb films were deposited on porous silicon substrates by physical vapor deposition (PVD) technique. Modulation effects due to the substrate on microstructure and magnetic properties of the MnSb film's were studied by scanning electron microscope (SEM), X-ray diffraction (XRD) and measurements of hysteresis loops. SEM images of the MnSb films indicate that net-like structures were obtained because of the special morphology of the substrates. The net-like MnSb films exhibit some novel magnetic properties different from the unpatterned referenced samples. For example, in the case of net-like morphology, the coercive field is as low as 60 Oe.

An Amino Acid Substitution Matrix for Protein Conformation Identification

Amino acid substitution matrices play an essential role in protein sequence alignment, a fundamental task in bioinformatics. Most widely used matrices, such as PAM matrices derived from homologous sequences and BLOSUM matrices derived from aligned segments of PROSITE, did not integrate conformation information in their construction. There are a few structure-based matrices, which are derived from limited data of structure alignment. Using databases PDB_SELECT and DSSP, we create a database of sequence-conformation blocks which explicitly represent sequence-structure relationship. Members in a block are identical in conformation and are highly similar in sequence. From this block database, we derive a conformation-specific amino acid substitution matrix CBSM60. The matrix shows an improved performance in conformational segment search and homolog detection.

Flow Stress of Biomorphous Metal-Matrix Composites

For metal-matrix composites (MMCs), interfacial debonding between the ductile matrix and the reinforcing hard inclusions is an important failure mode. A fundamental approach to improving the properties of MMCs is to optimize their microstructure to achieve maximum strength and toughness. Here, we investigate the flow stress of a MMC with a nanoscale microstructure similar to that of bone. Such a 'biomorphous' MMC would be made of staggered hard and slender nanoparticles embedded in a ductile matrix. We show that the large aspect ratio and the nanometer size of inclusions in the biomorphous MMC lead to significantly improved properties with increased tolerance of interfacial damage. In this case, the partially debonded inclusions continue to carry mechanical load transferred via longitudinal shearing of the matrix material between neighboring inclusions. The larger the inclusion aspect ratio, the larger is the flow stress and work hardening rate for the composite. Increasing the volume concentration of inclusion also makes the biomorphous MMC more tolerant of interfacial damage.

Parameters Inversion of Fluid-Saturated Porous Media Based on Neural Networks

The multi-layers feedforward neural network is used for inversion of material constants of fluid-saturated porous media. The direct analysis of fluid-saturated porous media is carried out with the boundary element method. The dynamic displacement responses obtained from direct analysis for prescribed material parameters constitute the sample sets training neural network. By virtue of the effective L-M training algorithm and the Tikhonov regularization method as well as the GCV method for an appropriate selection of regularization parameter, the inverse mapping from dynamic displacement responses to material constants is performed. Numerical examples demonstrate the validity of the neural network method.